We prepared a series of one-dimensional conjugated-material-based nanofibers with different morphologies and donor/acceptor (D/A) compositions by electrospinning for efficient photocatalytic hydrogen evolution. It was found that homogeneous D/A heterojunction nanofibers can be obtained by electrospinning, and the donor/acceptor ratio can be easily controlled. Compared with the single-component-based nanofibers, the D/A-based nanofibers showed a 34-fold increase in photocatalytic efficiency, attributed to the enhanced exciton dissociation in the nanofibrillar body. In addition, the photocatalytic activity of these nanofibers can be easily optimized by modulating the diameter. The results show that the diameter of the nanofibers can be conveniently controlled by the electrospinning feed rate, and the photocatalytic effect increases with decreasing fiber diameter. Consequently, the nanofibers with the smallest diameter exhibit the most efficient photocatalytic hydrogen evolution, with the highest release rate of 24.38 mmol/(gh). This work provides preliminary evidence of the advantages of the electrospinning strategy in the construction of D/A nanofibers with controlled morphology and donor/acceptor composition, enabling efficient hydrogen evolution.